EP0908230A2 - Absorptionsmittel für Stickoxide und dessen Verwendung zur Reinigung von Belüftungsgas - Google Patents

Absorptionsmittel für Stickoxide und dessen Verwendung zur Reinigung von Belüftungsgas Download PDF

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Publication number
EP0908230A2
EP0908230A2 EP98402525A EP98402525A EP0908230A2 EP 0908230 A2 EP0908230 A2 EP 0908230A2 EP 98402525 A EP98402525 A EP 98402525A EP 98402525 A EP98402525 A EP 98402525A EP 0908230 A2 EP0908230 A2 EP 0908230A2
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EP
European Patent Office
Prior art keywords
nitrogen dioxide
dioxide absorbent
mol
carrier
amino acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98402525A
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English (en)
French (fr)
Other versions
EP0908230A3 (de
EP0908230B1 (de
Inventor
Masayoshi C/O Hitachi Zosen Corporation Ichiki
Yuki c/o Hitachi Zosen Corporation Sairyo
Atsushi C/O Hitachi Zosen Corporation Fukuju
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Hitachi Zosen Corp
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Hitachi Zosen Corp
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Publication date
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Publication of EP0908230A2 publication Critical patent/EP0908230A2/de
Publication of EP0908230A3 publication Critical patent/EP0908230A3/de
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Publication of EP0908230B1 publication Critical patent/EP0908230B1/de
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
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    • Y10S95/90—Solid sorbent

Definitions

  • the present invention relates to a nitrogen dioxide (NO 2 ) absorbent or adsorbent for automotive exhaust gas purifying facilities to remove NO 2 by absorption or adsorption from ventilation gas discharged from road tunnels which contains nitrogen oxides (NO x ) in low concentrations.
  • NO 2 nitrogen dioxide
  • NO 2 which is an acidic gas
  • a conceivable common way of removing by absorption NO 2 (which is an acidic gas) from NO x -containing gas is by reaction with alkali for fixation into nitrate or nitrite. In actual, however, very little NO 2 is absorbed when air containing several ppm of NO 2 is bubbled in an aqueous solution of KOH.
  • NO 2 in very low concentrations as above can be absorbed and removed effectively by the use of a solid absorbent consisting of a porous carrier (such as titania or alumina which has solid acid properties) and KOH impregnated into and supported on the carrier, which had previously been proposed by the present inventors. (See Japanese Patent Laid-open No. 211427/1998.)
  • the present inventors studied in detail the nitrogen dioxide absorbent composed of a carrier of solid acid or activated carbon and a hydroxide of strong alkali (such as K and Na) supported thereon. As the result, they found the following problems involved in it.
  • NO 2 in the gas phase is adsorbed at the active sites of the catalyst and is denatured there into a form readily reactive with alkali.
  • the denatured product rapidly reacts with alkali hydroxide near the active site, and the resulting nitrate and nitrite are retained stably.
  • the active site of the catalyst becomes vacant, and the cycle of adsorption-denaturation can be repeated.
  • nitrate or nitrite has its anions (NO 3 - or NO 2 - ) dispersed into the vicinity from near the active site.
  • free alkali is regenerated near the active site, and it repeats its reaction with the denatured product forming at the active site.
  • the present inventors had previously proposed a carrier of titania (TiO 2 ) impregnated with a manganese (Mn) salt, followed by drying and firing.
  • This carrier meets the requirement of (a), or it has a catalytic action for denaturation of NO 2 . See Japanese Patent Laid-open No. 192049/1996.
  • the present inventors had also proposed a nitrogen dioxide absorbent employing a carrier impregnated with a hydroxide of alkali metal (such as K and Na). See Japanese Patent Laid-open No. 211427/1998.
  • the above-mentioned absorbent was capable of efficient absorption of NO 2 in low concentrations (1 ppm or below). This was a remarkable improvement as expected. However, it was found that the rate of absorption of NO 2 in low concentrations rapidly decreases according as NO 2 accumulates on the surface of the absorbent. See Fig. 5. A probable reason for this is that strong alkali nitrate or nitrite is so stable that it does not permit its anions (NO 2 - or NO 3 - ) to readily diffuse from near the active site, with the result that free alkali rapidly decreases near the catalytic active site.
  • the present inventors looked for an alkali which meets the requirement of (c). As the result, they found that desired characteristic properties are obtained by a basic amino acid, particularly arginine, and an organic amine compound, particularly guanidine.
  • the nitrogen dioxide absorbent is produced by a process which comprises impregnating a porous carrier sequentially with two aqueous solutions each containing a basic amino acid, for example, in an amount of 0.5-3.0 mol/l, preferably 1.0-2.0 mol/l, and an organic amine compound in an amount of 0.5-3.0 mol/l, preferably 1.0-2.0 mol/l, or with one aqueous solution containing a basic amino acid in an amount of 0.5-3.0 mol/l, preferably 1.0-2.0 mol/l, and/or an organic amine compound in an amount of 0.5-3.0 mol/l, preferably 1.0-2.0 mol/l.
  • impregnation is followed by drying at a temperature of 150°C or below, preferably 100°C or below.
  • the nitrogen dioxide absorbent is also produced by a process which comprises impregnating a porous carrier with an aqueous solution containing a basic amino acid in an amount of, for example, 0.5-2.0 mol/l, preferably 0.8-1.5 mol/l, an organic amine compound in an amount of 0.5-3.0 equivalents, preferably 0.8-2.0 equivalents (based on the carboxylic acid of the amino acid), and/or an alkali hydroxide in an amount of 0.5-3.0 equivalents, preferably 0.8-2.0 equivalents (based on the carboxylic acid of the amino acid).
  • impregnation is followed by drying at a temperature of 150°C or below, preferably 100°C or below.
  • the porous carrier is a porous oxide having solid acid properties.
  • the porous oxide having solid acid properties includes, for example, alumina, silica ⁇ alumina, titania, and zeolite. They can be used alone or in combination with one another.
  • a preferred example of the porous carrier is a porous oxide carrying one or more metals selected from the group consisting of Mn, Co, Fe, and Ni. It is produced by impregnating a porous oxide with an aqueous solution containing (or solutions each containing) inorganic acid salts (excluding sulfates) or organic acid salts of said metals in an amount of 0.5-5 mol/l, preferably 2-4 mol/l, at one time or sequentially.
  • the porous oxide should have a specific surface area of 30-500 m 2 /g, preferably 60-120 m 2 /g.
  • the porous oxide can be held in interstices between fibers of preform in the form of plate or honeycomb.
  • porous carrier is activated carbon.
  • This activated carbon should have a specific surface area of 100-2000 m 2 /g, preferably 300-600 m 2 /g.
  • the activated carbon should preferably be in the form of honeycomb.
  • the basic amino acid should preferably be arginine
  • the organic amine compound should preferably be guanidine.
  • the alkali hydroxide should preferably be one or more than one member selected from lithium hydroxide, potassium hydroxide, and sodium hydroxide.
  • the nitrogen dioxide absorbent constructed as mentioned above is suitable for purification of ventilation gas discharged from road tunnels. It is capable of absorbing and removing NO 2 from ventilation gas passing at a flow rate of 0.05-10.0 Nm/s (in terms of superficial velocity).
  • the present inventors have developed a new nitrogen dioxide absorbent composed of a carrier of solid acid or activated carbon having an additional denaturing catalytic action on NO x and a basic amino acid or guanidine supported thereon which is solid at normal temperature and has a very low vapor pressure.
  • the basic amino acid or guanidine bonds strongly to a solid acidic oxide as the carrier and becomes adsorbed strongly by activated carbon.
  • the nitrogen dioxide absorbent of the present invention is composed of a carrier of solid acid or activated carbon and a basic amino acid or guanidine supported thereon. It functions as an excellent nitrogen dioxide absorbent which can be used under severe conditions as mentioned above.
  • An amino acid usually has an amino group (basic) and a carboxyl group (acid).
  • the former serves to fix NO 2 , but the latter does not.
  • Arginine and guanidine vaporize less than other organic amine compounds and hence are highly capable of fixing NO 2 .
  • the carboxyl group in arginine is close to the amino group as the structural formula [I] shows below. It does not serve to fix NO 2 , but it also prevents the diffusion of NO 3 - , NO 2 - , etc. from one amino group to another.
  • this carboxyl group effectively fixes NO 2 , thereby increasing the absorbing capacity of the absorbent.
  • guanidine shown by the formula [II] below as the basic compound provides only amino groups useful for the diffusion of NO 2 ; therefore, it reduces the factor to prevent the diffusion.
  • preferred nitrogen dioxide absorbent is obtained by preparing a titania carrier incorporated with Mn and then impregnating the carrier with an aqueous solution containing arginine and alkali hydroxide or guanidine in approximately equimolar amounts, followed by drying.
  • the alkali hydroxide or guanidine should be used in an amount slightly more than arginine because it reacts directly with the acid site of the carrier.
  • the absorbing capacity for NO 2 increases with the increasing amount of arginine supported; however, an excess amount of arginine clogs the pores of the catalyst and covers the active site of the catalyst, thereby decreasing the absorbing rate.
  • activated carbon has a larger specific surface area but a smaller pore diameter and hence a lower critical supporting amount (per specific surface area) which does not lower the absorbing rate.
  • the nitrogen dioxide absorbent of the present invention exhibits its essential functions by virtue of:
  • Fig. 1 is a graph showing the relation between the NO 2 /NO x ratio and the NO 2 removal ratio.
  • Fig. 2 is a graph showing the relation between the NO 2 concentration at the entrance and the NO 2 removal ratio.
  • Fig. 3 is a graph showing the relation between the adsorption time and the concentrations of NO and NO 2 .
  • Fig. 4 is a conceptual diagram showing the absorption of NO 2 on the surface of the nitrogen dioxide absorbent.
  • Fig. 5 is a graph showing the relation between the NO 2 concentration at the entrance and the NO 2 removal ratio.
  • Fig. 6 is a conceptual diagram showing the postulated surface structure of the nitrogen dioxide absorbent.
  • Fig. 7 is a graph showing the relation between the amount of NO 2 absorption and the ratio of NO 2 absorption.
  • Fig. 8 is a graph showing the relation between the amount of NO 2 absorption and the ratio of NO 2 absorption.
  • titania is used as the solid acid carrier and pitch-based activated carbon is used as the activated carbon; however, the use of these carriers is not intended to limit the nitrogen dioxide absorbent of the present invention.
  • Rate of NO 2 absorption (A - B)/A ⁇ 100 where,
  • a standard gas of the composition shown in Table 1 was passed through the absorbing tube at a flow rate of 4 l/min, and the rate of absorption (initial performance) was measured.
  • the results are shown in Table 3. It is noted that magnesium nitrate does not contribute to the rate of NO 2 absorption.
  • the lamellar carrier incorporated with Mn in Example 1 was given arginine and organic amine compound and/or alkali hydroxide in different concentrations (as shown in Table 4). Using this carrier, there were obtained nitrogen dioxide absorbents (K) to (T) in the same manner as in Example 1. These absorbents were tested for performance in the same manner as (b) in Example 1. Table 4 shows examples of concentrations of immersion solutions and NO 2 absorption performance.
  • the activated carbon carrier was given arginine and organic amine compound and/or alkali hydroxide in the same way as in Example 2.
  • nitrogen dioxide absorbents (AC-1) to (AC-7) were tested for performance.
  • the samples were cut into smaller pieces, each measuring 20 mm ⁇ 20 mm ⁇ 25 mm, so that the rate of NO 2 absorption was low.
  • the results are shown in Table 5.
  • Each of solid acid granular carriers (8 to 14 mesh in size) was immersed in an aqueous solution containing 3.0 mol/l of manganese nitrate for 30 minutes, followed by drying at 120° C in the air for 3 hours and firing at 400°C for 5 hours.
  • solid acid carriers incorporated with manganese. They were immersed in an aqueous solution containing 1.3 mol/l of L-arginine and 1.5 mol/l of guanidine for 30 minutes, followed by drying at 60°C in the air for 5 hours.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)
EP98402525A 1997-10-13 1998-10-12 Absorptionsmittel für Stickoxide und dessen Verwendung zur Reinigung von Belüftungsgas Expired - Lifetime EP0908230B1 (de)

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JP27832097 1997-10-13
JP27832097 1997-10-13
JP278320/97 1997-10-13
JP29406297 1997-10-27
JP294062/97 1997-10-27
JP29406297 1997-10-27
JP29515697 1997-10-28
JP29515697 1997-10-28
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EP2401054A2 (de) * 2009-02-26 2012-01-04 Corning Inc. Sorptionsmittelstruktur, die zum abfangen von kohlendioxid angewendet werden kann
CN109569739A (zh) * 2016-12-28 2019-04-05 苏州大学 基于二氧化钛的双层中空材料及其在硫化氢光催化处理中的应用

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US7238332B2 (en) * 2004-06-14 2007-07-03 Feaver William B Material and process for the filtration of nitric acid and NO2 from streams of air
WO2008067521A1 (en) 2006-11-30 2008-06-05 Purafil, Inc. Dry-scrubbing media compositions and methods of production and use
WO2009120744A1 (en) 2008-03-25 2009-10-01 Purafil, Inc. Dry-scrubbing media compositions and methods of production and use
US8500880B2 (en) * 2009-11-24 2013-08-06 Corning Incorporated Amino acid salt articles and methods of making and using them
US9403124B2 (en) * 2012-08-02 2016-08-02 Siemens Aktiengesellschaft Method for reducing the concentration of nitrogen dioxide
US10011503B2 (en) * 2014-07-22 2018-07-03 Corning Incorporated Method for making activated carbon-supported transition metal-based nanoparticles
CN104415756A (zh) * 2013-08-22 2015-03-18 上海郎特电力环保科技有限公司 一种改性活性炭及其制备方法
CN104415755A (zh) * 2013-08-22 2015-03-18 上海郎特电力环保科技有限公司 一种以改性活性炭为基体材料的脱硝催化剂及其制备方法
CN106422698A (zh) * 2016-08-24 2017-02-22 江苏华晖环保科技有限公司 一种改进型物化生化一体化脱硫脱硝设备
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CN109569739A (zh) * 2016-12-28 2019-04-05 苏州大学 基于二氧化钛的双层中空材料及其在硫化氢光催化处理中的应用

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DE69832678D1 (de) 2006-01-12

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